Covalent Organic Polymers (COPs)

COPs are porous network polymers that have permanent pores. These permanent voids (mostly in nanoporous region, pore sizes below 100 nm) bring porous material properties such as gas capture and separation, water treatment and catalysis. Below is a list of COPs made in our labs. For a complete list of similar porous polymers please visit our porous polymers collection.


In a typical synthesis of a COP, cores and linkers are bound via an organic coupling reaction, preferably one that is made of sustainable components and conditions, e.g. no rare earth catalysts or non-trivial experimental setup and parameters. Most COPs are amorphous insoluble powders with few exceptions. 



COP-1
The first ever COP we synthesized. Features Triazine core, piperazine linkers. No 2D layers detected. An amorphous, 3D arrangement yields very low density (tapped bulk density: 0.127 g/cm3) and moderate surface area (168 m2/g) with significant gas capture capacity, as high as 5616 mg/g (127.6 mmol/g) CO2 at 200 bar and 45 oC. This capacity marks one of the highest ever CO2 capacity measured in a porous material.


Reference: Patel et al, J. Mater. Chem., 22, 8431-8437, (2012)

COP-2
The second COP in our library features a triazine core that is linked with bipiperidines, following a similar architecture with that of COP-1. Lower surface area (158 m2/g) and microporosity (17.7 nm average pore size - compare it with 6.6 nm for COP-1) results in lower CO2 capacity, 2086 mg/g (47.4 mmol/g). This, however, helps in selectivity of CO2 against H2. COP-2 has very high selectivity to CO2 over H2.

ReferencePatel et al, J. Mater. Chem., 22, 8431-8437, (2012)

COP-3
(Sulfur-COP-1 or S-COP-1)
Third COP we made features highly stable sulfur linkages. With a reasonably high surface area (BET = 413 m2 g-1), COP-3 adsorbs 74 mg CO2 /g (or 1.7 mmol g-1) at 273 K and 1 bar. Because the system is highly conjugated, one expects feasible electronic properties. It has a wide band-gap of Eg = 3.68 eV.

Reference: Patel et al., Adv. Funct. Mater., 23, 2270–2276 (2013).

COP-4
(Sulfur-COP-2 or S-COP-2)
Similar to COP-3, COP-4 also made out of sulfur-triazine coupling reactions. Its surface area is moderate at best (BET = 54 m2 g-1) and CO2 capacity is 33 mg g-1 (0.75 mmol/g) at 273 K and 1 bar. Also shows a wide band-gap of Eg = 3.57 eV.

ReferencePatel et al., Adv. Funct. Mater., 23, 2270–2276 (2013).

COP-5
(Sulfur-COP-3 or S-COP-3)
Triazines binding to biphenyl dithiol linkers form COP-5. The surface area is higher than COP-4 (at a BET value of 75 m2 g-1), as one would expect the linker's contribution to the extension of pores. CO2 capacity is lower, however, at 24 mg g-1 ( 0.55 mmol/g, 273 K, 1 bar). Band gap is also larger, Eg = 3.8 eV.

ReferencePatel et al., Adv. Funct. Mater., 23, 2270–2276 (2013).

COP-6
(Sulfur-COP-4 or S-COP-4)
COP-6 is made from highly available building blocks, the cyanuric chloride core and 4,4'-thiobisbenzenethiol linker. Its surface are is a mere 15 m2 g-1 (BET) which yields a low CO2 capacity of 20 mg g-1 (0.45 mmol/g) at 273 K and 1 bar. Also features a wide band gap of Eg = 3.5 eV.

ReferencePatel et al., Adv. Funct. Mater., 23, 2270–2276 (2013).

COP-65
(Disulfide-COP-3)

Reference: Patel et al., RSC Adv., 4 (46), 24320 - 24323, (2014).


COP-66
(Disulfide-COP-4)


Reference: Patel et al., RSC Adv., 4 (46), 24320 - 24323, (2014).


COP-68
(Azo-COP-1)
Made from a metal catalyst free coupling of tetra-anilyl-methane and tetra-nitrobenzyl-methane, COP-68 features azo linkages. Highly porous (BET = 635 m2 g-1) nature brings high CO2 uptake, 107.6 mg g-1 at 273 K and 1 bar. Azo-COPs also show a unique N2-phobic behavior, leading to very high CO2/N2 selectivities at elevated temperatures (171 at 323 K). Highly aromatic, conjugated framework exhibits a band-gap of 2.22 eV.

Reference: Patel et al., Nat. Commun., 4:1357, (2013)

COP-69
(Azo-COP-2)
Synthesized in identical conditions with COP-68, COP-69 is also an Azo-COP featuring azo (-N=N-) groups. It has the highest surface area of all COPs with a BET SA of 729 m2 g-1. Hence, the highest CO2 uptake at low pressures with 112.4 mg g-1 (2.55 mmol/g) at 273 K and 1 bar. Also N2-phobic, Azo-COP-2 also has very high CO2/N2 selectivity of 288 (at 50 oC). It's band gap is 2.35 eV.

Reference: Patel et al., Nat. Commun., 4:1357, (2013)

COP-70 
(Azo-COP-3)
The third in Azo-COP series, COP-70 is made via the same coupling reaction of amine and nitro building blocks. It's surface area is unexpectedly low, BET = 493 m2 g-1, when compared to other Azo-COPs. Nonetheless, it is still in the top 10 highest surface area among all COPs. CO2 capacity is formidable, at 85.1 mg g-1 (1.94 mmol/g) at 273 K and 1 bar. CO2/N2 selectivity is 163 at 50 oC. The bandgap is 2.34 eV.

Reference: Patel et al., Nat. Commun., 4:1357, (2013)

COP-72
(Azo-COP-4)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-73
(Azo-COP-5)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-74
(Azo-COP-6)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-75
(Azo-COP-7)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-76
(Azo-COP-8)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-77
(Azo-COP-9)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-79
(Azo-COP-10)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-81
(Azo-COP-11)

Reference: Patel et al., Chem. Eur. J., 20, 772-780, (2014).

COP-83
(Troger-COP-1)

Reference: Byun et al., J. Mater. Chem. A, 2, 12507-12512, (2014).

COP-84
(Troger-COP-2)

Reference: Byun et al., J. Mater. Chem. A, 2, 12507-12512, (2014).

COP-85
(Ionic-COP-1)

Reference: Raja et al., RSC Adv. 4 (104), 59779 - 59784 (2014)

COP-86
(iCOP-2)

Reference: Raja et al., RSC Adv. 4 (104), 59779 - 59784 (2014)

COP-87
(iCOP-3)

Reference: Raja et al., RSC Adv. 4 (104), 59779 - 59784 (2014)

COP-88
(iCOP-4)

Reference: Raja et al., RSC Adv. 4 (104), 59779 - 59784 (2014)

COP-89
(iCOP-5)

Reference: Raja et al., RSC Adv. 4 (104), 59779 - 59784 (2014)

COP-90
(iCOP-6)

Reference: Raja et al., RSC Adv. 4 (104), 59779 - 59784 (2014)
***
Click here for all of our research papers that report COPs

***
List of unpublished COPs:

COP–7
BET = 15 m2 g-1
COP–8
BET = 19 m2 g-1
COP–9
BET = 146 m2 g-1
COP–10
BET = 97 m2 g-1
COP–11
BET = 36 m2 g-1 ; Eg = 3.6 eV
COP–13
BET = 70 m2 g-1
COP–15
BET = 44 m2 g-1
COP–16
BET = 27 m2 g-1
COP–19
BET = 600 m2 g-1
COP–20
BET = 0.75 m2 g-1; Eg = 1.75 eV
COP–21
BET = 13.8 m2 g-1; Eg = 2.12 eV
COP–22
BET = 6 m2 g-1; Eg = 2.76 eV
COP–25
BET = 34.5 m2 g-1
COP–28
BET = 33.8 m2 g-1
COP–32
BET = 46 m2 g-1
COP–33
BET = 53 m2 g-1
COP–34
BET = 33.4 m2 g-1
COP–37
BET = 54.2 m2 g-1
COP–39
BET = 66.6 m2 g-1
COP–40
BET = 1.1 m2 g-1; Eg = 2.26 eV
COP–41
BET = 44.6 m2 g-1
COP–42
BET = 22.7 m2 g-1
COP–43
BET = 33.3 m2 g-1
COP–44
BET = 24.5 m2 g-1
COP–45
BET = 16 m2 g-1
COP–48
BET = 29.2 m2 g-1
COP–49
BET = 42.8 m2 g-1; Eg = 3.3 eV
COP–50
BET = 25.2 m2 g-1; Eg = 2.02 eV
COP–51
BET = 1.5 m2 g-1; Eg = 2.43 eV
COP–52
BET = 11.2 m2 g-1; Eg = 2.6 eV
COP–63
BET = 194 m2 g-1
COP–64
BET = 4.8 m2 g-1
COP–71
BET = 105.5 m2 g-1
COP–72
BET = 11.4 m2 g-1
CO2 = 77.4 mg g-1 at 273 K & 1 bar
COP–73
BET = 152.7 m2 g-1
CO2 = 89.7 mg g-1 at 273 K & 1 bar
COP–74
BET = 711 m2 g-1
CO2 = 97.6 mg g-1 at 273 K & 1 bar
COP–75
BET = 268.5 m2 g-1
CO2 = 83.9 mg g-1 at 273 K & 1 bar
COP–76
BET = 520.5 m2 g-1
CO2 = 89.1 mg g-1 at 273 K & 1 bar
COP–77
BET = 563.6 m2 g-1
CO2 = 90 mg g-1 at 273 K & 1 bar
COP–79
BET = 173.1 m2 g-1
CO2 = 84 mg g-1 at 273 K & 1 bar
COP–80
BET = 8.6 m2 g-1
CO2 = 42.8 mg g-1 at 273 K & 1 bar
COP–81
BET = 288.5 m2 g-1
CO2 = 93.6 mg g-1 at 273 K & 1 bar


* When we first designated, the COP abbreviation stood for Cyanuric Organic Polymers, because of the triazine cores of early COPs. Since we moved beyond triazines, the name evolved into a general description at the expense of specificity but preserving the list. The abbreviation also fits to Crystalline Organic Polymers, which we recently started making.

 
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